Synthesis of Mono-N-Methyl Aromatic Amines from Nitroso Compounds and Methylboronic Acid

Abstract

The selective synthesis of mono- N -methyl aromatic amines was achieved by the reaction of aromatic nitroso compounds with methylboronic acid promoted by triethylphosphite under transition metal-free conditions. The target compounds are constructed efficiently without overmethylation, under environmentally benign reaction conditions that do not require bases or reductants and therefore are of interest in pharmaceutical, agricultural, and chemical industries.

Iron-Catalyzed Benzene Ring Expansion of α-Azido-N-phenylamides

“…Cyclopropylanilines (Method A) 24 P(OEt) 3 (1.9 mL, 11.0 mmol) was added to a solution of nitrosobenzene (1.1 g, 10.0 mmol) and cyclopropylboronic acid (1.1 mL, 15.0 mmol) in toluene (30 mL) contained in a 100-mL round-bottom flask equipped with a magnetic stirring bar. The mixture was stirred at r.t. for 20 min.…”

Fe3O4@GlcA@Cu-MOF: A Magnetic Metal–Organic Framework as a Recoverable Catalyst for the Hydration of Nitriles and Reduction of Isothiocyanates, Isocyanates, and Isocyanides

“…Moreover, these compound may be achieved from carboxylic acids via utilization of acyl azides as amine surrogate and methanol as carbon source (Scheme 3C), 38 from methylamine and functionalized aryl electrophiles under transition-metal catalysis (Scheme 3D). 39 Lastly, the reaction of aromatic nitroso compounds with methylboronic acid promoted by triethylphosphite (Scheme 3E) 40 and the catalytic reduction of isonitriles with hydrogen (Scheme 3F) 41 have also been reported.…”

Room-Temperature CuI-Catalyzed N-Arylation of Cyclopropylamine

“…C{1 H} NMR (150 MHz, DMSO-d 6 ) δ 153.0, 133.3, 120.7, 112.3, 96.3, 24.0, 6.8.N-Cyclopropyl-4-fluoroaniline (3h) 55. Colorless oil, 143 mg, yield: 95%, eluting with petroleum ether/ethyl acetate (30:1).…”